JP2023536379A - Organic-inorganic hybrid complex and coating composition containing the same, separator, secondary battery, battery module, battery pack and power consumption device - Google Patents

Abstract

The present application provides an organic-inorganic hybrid complex that can be applied to a separator coating for secondary batteries, and this organic-inorganic hybrid complex has basic units represented by formula (I) arranged along at least one spatial direction. The defect percentage represented by i/x*100% in the formula [Lx-i□i][MaCb].Az(I) is from 1% to 30%. The present application further provides a coating composition including this complex, a coating formed with this coating composition, a separator for a secondary battery including this coating, and a secondary battery, battery module, battery pack, and device including this separator. do. By applying the organic-inorganic hybrid complex of the present application to the coating, the electrolyte permeability of the separator for secondary batteries is improved, and the electrolyte retention rate is improved, thereby improving the rate performance and cycle of the secondary battery. Improve lifespan.

Description

The present application relates to the field of secondary battery technology, and more particularly to possible organic-inorganic hybrid complexes for forming coatings on secondary battery separators, coating compositions comprising these complexes, coatings formed with these coating compositions, The present invention relates to a secondary battery separator including a coating, and a secondary battery, battery module, battery pack and power consumption device including the separator.

Lithium-ion secondary batteries have advantages such as high energy density, long cycle life and no memory effect, and are widely applied in many consumer electronic products. In recent years, with the continuous development of electric vehicles and energy storage systems, the demand for the energy density of lithium-ion secondary batteries has also increased.

A secondary battery refers to a battery that can be used continuously by activating the active material by charging after the battery is discharged. A secondary battery typically includes a positive plate, a negative plate, a separator, an electrolyte, and a solvent. During the charging and discharging process of the battery, active ions are intercalated and deintercalated between the positive and negative plates. A separator is installed between the positive electrode plate and the negative electrode plate. A separator is an important component of a lithium-ion battery and is usually a polymeric functional material with nanoscale pores. The main function of the separator is to allow electrolyte ions to pass through and to prevent short circuits due to contact between the two electrodes. Specifically, the separator can insulate against electrons, prevent internal short circuits, and allow active ions to permeate and move between the positive and negative electrodes. Since the performance of the separator determines the interfacial structure and internal resistance of the battery, it directly affects the capacity, cycle and safety performance of the battery.

At present, commercialized lithium-ion battery separator products mostly use polyolefin materials, especially polyolefin microporous membranes. PP/PE/PP multi-layer microporous membrane formed compositely. These polyolefin microporous membranes have poor electrolyte wettability, causing pouring difficulties during production and increased polarization, reducing battery power density and cycle life.

In the prior art, ion-conducting coatings, such as ceramic coatings, have been used to improve wettability. However, the production of these coatings requires baking, the process is complicated, and the effect of improving wettability is particularly limited, so the effect of improving battery rate performance and cycle life is insufficient. be. In addition, high temperature resistant metal-organic frame materials (MOFs) have been used as the main coating material to improve wettability. However, when MOF material coatings are used to improve the wettability of the separator, such improvement depends only on the increase in separator porosity, i.e., the increase in specific surface area, and in fact the contribution from the material itself. is very low, the wettability of MOF material-coated separators still needs to be improved.

In view of the above-mentioned problems existing in the background art, the present application has the effect of improving electrolyte wettability, reduces polarization by improving electrolyte retention rate, and improves power density of secondary batteries. It is an object of the present invention to provide a coating material used for a secondary battery separator that can extend the cycle life.

In order to achieve the above object, as one aspect, the present application provides an organic-inorganic hybrid complex, wherein the organic-inorganic hybrid complex comprises at least one space It is constructed by cyclically assembling along the direction.
[L _x−i □ _i ][M _a C _b ]·A _z (I)

However, in formula (I), M represents the first transition metal element, C optionally represents an atom, atomic group, or anion capable of forming a metal cluster with M, and L represents a metal M or a metal represents an organic ligand capable of forming a coordinate bond with the cluster M _a C _b , especially an organic bridging ligand, □ represents a ligand defect, and A represents an atom or cation capable of occlusion and release. x can take a number from 1 to 4, and can also optionally take a number from 1 to 3, and a can take a number greater than 0 and up to and including 4, and further optionally , may take a number from 1 to 4. z may take a number from 0 to 2, and optionally from 0 to 1. In formula (I), the relationships 0<i<x and 0≤b:a≤1 may be satisfied.

In this application, defect percentage i/x*100% is used to express the degree of defect of the organic-inorganic hybrid complexes of this application relative to an ideal defect-free crystalline structure. The defect percentage may be from about 1% to about 30%.

In one embodiment, the defect percentage may be from about 2% to about 20%. In one embodiment, the defect percentage may be from about 2.5% to about 18%. In one embodiment, the defect percentage may be from about 5% to about 10%.

In one embodiment, in formula (I), the relationship 1/2≦x:a≦3 may be satisfied.

In one embodiment, in formula (I), the ratio between a and b may satisfy 1/4≦b:a≦1.

In one embodiment, M may be selected from one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. Further optionally, M may be selected from one or more of Mn, Fe, Co, Cu and Zn.

In one embodiment, C is selected from one or more of -O-, =O, ^O2- , ^{S2- ,} F-, ^Cl- , Br- ^{, I-} , CO, -OH and ^OH- may be More optionally, C may be -O- or -OH.

In one embodiment, the organic bridging ligand L is a cyano group, a benzimidazole-based ligand, a porphyrin-based ligand, a pyridine-based ligand, a pyrazole-based ligand, a pyrimidine-based ligand, a piperidine-based ligand. pyrrolidine-based ligands, furan-based ligands, thiophene-based ligands, pyrazine-based ligands, piperazine-based ligands, pyridazine-based ligands, triazine-based ligands, tetrazine-based ligands, It may be selected from at least one of indole-based ligands, quinoline-based ligands, morpholine-based ligands, carbazole-based ligands, and polycarboxylic acid-based ligands. One or more hydrogen atoms in said organic bridging ligand L are optionally substituted with one or more substituents, said substituents being respectively a cyano group, a nitro group, an amino group, an aldehyde group, carboxyl group, halogen, C1-C6 alkoxy group, C1-C6 hydroxyalkyl group, C1-C6 alkoxy group, C2-C6 alkenyl group, C2-C6 alkynyl group, C3-C8 cycloalkyl group, C6-C10 aryl group, C6 may be independently selected from at least one of -C10heteroaryl groups and any combination thereof. In one embodiment, the organic bridging ligand L may be selected from at least one of a cyano group, a benzimidazole-based ligand and a polycarboxylic acid-based ligand. In one embodiment, the organic bridging ligand L may be selected from at least one of a cyano group, a benzimidazole-based ligand, a trimesic acid-based ligand and a terephthalic acid-based ligand. In one embodiment, the organic bridging ligand L is a cyano group, 5-chlorobenzimidazole ligand (cbIm), trimesic acid ligand (BTC), terephthalic acid ligand (BDC) and tris(2-benz imidazolmethyl)amine ligands (NTB).

In one embodiment, A may be selected from atoms or cations of one or more of the metallic elements Li, Na, K, Rb, Cs, Sr, Zn, Mg and Ca. Further optionally, A may be Li or Na.

In one embodiment, in the organic-inorganic hybrid complexes of the present application, the base unit represented by formula (I) is periodic along at least one of the three spatial directions X', Y' and Z' wherein the three directions X', Y' and Z' respectively form angles of 0 to 75 degrees with the X, Y and Z directions of a Cartesian coordinate system; is an angle between 5 and 60 degrees.

In one embodiment, the basic units represented by formula (I) may be assembled periodically along at least one spatial direction of the X, Y and Z directions of a Cartesian coordinate system.

In one embodiment, in the organic-inorganic hybrid complexes of the present application, the number of base units of formula (I) assembled periodically along at least one spatial direction is from about 3 to about 10,000. may be

On the other hand, the present application further provides a coating composition for use in secondary battery separators, said coating composition may comprise the organic-inorganic hybrid complex of the present application as described above.

In one embodiment, the coating composition of the present application may contain from about 12 wt% to about 90 wt% of the organic-inorganic hybrid complex based on the total weight of the coating composition. In one embodiment, the content of the organic-inorganic hybrid complex may be from about 17 wt% to about 85 wt%, based on the total weight of the coating composition. In one embodiment, the content of the organic-inorganic hybrid complex may be from about 34 wt% to about 68 wt%, based on the total weight of the coating composition.

In one embodiment, optionally, the coating composition of the present application may further comprise inorganic particles.

In one embodiment, when the coating composition of the present application contains inorganic particles, the mass ratio of the organic-inorganic hybrid complex to the total mass of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be from about 15 wt% to about 85 wt%. In one embodiment, the weight ratio of the organic-inorganic hybrid complex to the total weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be from about 20 wt% to about 80 wt%. In one embodiment, the weight ratio of the organic-inorganic hybrid complex to the combined weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be from about 40 wt% to about 80 wt%.

In one embodiment, when inorganic particles are included in the coating composition of the present application, the inorganic particles are boehmite, zeolites, molecular sieves, alumina, aluminum oxyhydroxide, silicon dioxide, aluminum nitride, silicon carbide, magnesium oxide, calcium oxide. , zinc oxide, zirconium oxide, titanium oxide and mixtures thereof.

On the other hand, the present application further provides a separator for secondary batteries. The secondary battery separator of the present application comprises a polymer substrate layer and a coating applied onto the substrate layer, wherein the coating comprises the organic-inorganic hybrid complex of the present application as described above or may comprise the coating composition of the present application as described in .

On the other hand, the present application further provides a secondary battery. The secondary battery of the present application may include a positive electrode, a negative electrode, an electrolyte, and the secondary battery separator of the present application described above.

On the other hand, the present application further provides a battery module. The battery module of the present application may include the secondary battery of the present application described above.

On the other hand, the present application further provides a battery pack. The battery pack of the present application may include the battery module of the present application described above.

On the other hand, the present application further provides a power consumption device. The power consumption device of the present application may include the secondary battery of the present application described above, the battery module of the present application described above, the battery pack of the present application described above, or a combination thereof.

In the secondary battery of the present application, by applying the organic-inorganic hybrid type complex of the present application to the coating of the separator, the electrolyte wettability of the separator is significantly improved, and the electrolyte retention rate is greatly improved. This reduces the polarization and ultimately improves the power density and cycle life of the secondary battery significantly.

1 is a schematic diagram of a secondary battery of one example of the present application; FIG. FIG. 2 is an exploded view of the secondary battery of one embodiment of the present application shown in FIG. 1; 1 is a schematic diagram of a battery module of one embodiment of the present application; FIG. 1 is a schematic diagram of a battery pack of one embodiment of the present application; FIG. FIG. 5 is an exploded view of the battery pack of one embodiment of the present application shown in FIG. 4; 1 is a schematic diagram of an apparatus using a secondary battery as a power source in one embodiment of the present application; FIG. 2 is an SEM photograph of the material obtained in Production Example 1. FIG. 1 is an SEM photograph of a separator having a coating obtained in Example 1; Fig. 2 is a wettability test photograph of the separators of Control Example 1, Comparative Example 1 and Example 1 obtained in Test Example 1; 5 is a graph of cycle performance of battery cells of Control Application Example 1, Comparative Application Example 1, and Application Example 1 obtained in Test Example 5. FIG.

In order to make the purpose, technical solution and advantages of the present application clearer, the embodiments of the application are described in detail below in conjunction with the accompanying drawings. However, as can be understood by those skilled in the art, these examples are only used to describe the technical solution of the present application and are not intended to be limiting.

For the sake of simplicity, this application specifically discloses some numerical ranges. However, any lower limit may be combined with any upper limit to form a range not explicitly stated, and any lower limit may be combined with any other lower limit not explicitly stated Ranges may be formed and, similarly, any upper limit may be combined with any other upper limit to form ranges not explicitly recited. It should be noted that each independently disclosed point or individual numerical value by itself is expressly recited as a lower or upper limit, in combination with any other point or individual numerical value, or in combination with any other lower or upper limit. may form a range that is not

Unless otherwise stated, all embodiments and selective embodiments of the present application can be combined with each other to form new technical solutions.

All technical features and optional technical features of the present application can be combined with each other to form new technical solutions unless otherwise stated.

Unless otherwise stated, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method comprising steps (a) and (b) may comprise steps (a) and (b) performed sequentially, and steps (b) and (a) performed sequentially. and may be included. For example, the method referred to above further comprising step (c) represents that step (c) may be added to the method in any order, e.g., the method may comprise step (a ), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and so on.

Unless otherwise stated, the terms “include” and “include” referred to in this application are open and may be closed. For example, the terms "comprising" and "including" may indicate that it may further include or include other ingredients not listed, or it may include or include only the listed ingredients. .

Unless otherwise stated, in this application the term "or" is inclusive. For example, the term "A or B" represents "A, B, or both A and B." More specifically, the condition that A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exists) ) or that both A and B are true (or exist) satisfy the condition "A or B".

In one aspect, the present application provides organic-inorganic hybrid complexes. The organic-inorganic hybrid complexes of the present application may be constructed by periodically assembling basic units represented by formula (I) along at least one spatial direction.
[L _x−i □ _i ][M _a C _b ]·A _z (I)

In formula (I), M can represent the first transition metal element. The first transition metal element has active chemical properties, has a stable low oxidation valence (+1 to +4), has relatively high electronegativity, and has strong coordination bonding ability. This is because the first transition metal element and an organic ligand (which may also be called an organic ligand) form a coordinate bond, or form a metal cluster, and then an organic ligand often seen. It favors the formation of coordinative bonds, resulting in high valences of +5 to +7, and also avoids causing too many coordinative bonds to be required in the neighboring space of the metal atom. The first transition metal element has a relatively small steric hindrance effect, is more likely to form a stable coordination structure, and forms a metal-metal bond like the second and third transition metal elements. , without thereby affecting the stability of the coordination bonds.

Optionally, M may be selected from one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. Further optionally, M may be selected from one or more of Mn, Fe, Co, Cu and Zn.

In formula (I), C optionally represents an atom, atomic group, or anion capable of forming a metal cluster with M. Optionally, C is selected from one or more of -O-, =O, ^O2- , ^{S2- ,} F-, ^Cl- , Br- ^, I- ^, CO, -OH and ^OH- may be More optionally, C may be -O- or -OH.

In formula (I), L represents an organic ligand, especially an organic bridging ligand, capable of forming a coordinate bond with the metal M or the metal cluster M _a C _b . Although the mechanism is not yet fully understood, compared to monodentate ligands (i.e., ligands containing one coordinating atom), organic bridging ligands are required to receive a certain proportion of defect sites. It has the potential to effectively provide complete metal-ligand frames. Such a complete frame structure can sufficiently achieve the effect of improving the wettability of the coating separator on the premise of maintaining the structural stability of the organic-inorganic hybrid complex.

As non-limiting examples, the organic bridging ligand L can be a cyano group (CN), a benzimidazole-based ligand, a porphyrin-based ligand, a pyridine-based ligand, a pyrazole-based ligand, a pyrimidine-based ligand. child, piperidine-based ligand, pyrrolidine-based ligand, furan-based ligand, thiophene-based ligand, pyrazine-based ligand, piperazine-based ligand, pyridazine-based ligand, triazine-based ligand, Tetrazine-based ligands, indole-based ligands, quinoline-based ligands, morpholine-based ligands, carbazole-based ligands and polycarboxylic acid-based ligands may be included. One or more hydrogen atoms in said organic bridging ligand L are optionally substituted with one or more substituents, said substituents being cyano, nitro, amino, aldehyde, carboxyl group, halogen, C1-C6 alkyl group, C1-C6 hydroxyalkyl group, C1-C6 alkoxy group, C2-C6 alkenyl group, C2-C6 alkynyl group, C3-C8 cycloalkyl group, C6-C10 aryl group, C6- It may be independently selected from C10 heteroaryl groups and any combination thereof.

As non-limiting examples, benzimidazole ligands include benzimidazole ligand (bIm), 5-chlorobenzimidazole ligand (cbIm), 5-nitrobenzimidazole ligand (nbIm), 2- Methyl-5-chlorobenzimidazole ligand, tris(2-benzimidazolemethyl)amine ligand (NTB), and the like may also be included. The imidazole-based ligands may include imidazole ligands (IM), 2-methylimidazole ligands (mIM), 2-nitroimidazole ligands (nIM), and the like. Pyrimidine-based ligands may include 2-hydroxy-5-fluoropyrimidine ligands (F-pymo). Triazine-based ligands may include 2,4,6-trimercapto-s-triazine ligand (TATB). Tetrazine-based ligands may include 3,6-di-4-pyridine-1,2,4,5-tetrazine ligands (DPT). Polycarboxylic acid ligands include pyromellitic acid ligand (BTEC), trimesic acid ligand (BTC), terephthalic acid ligand (BDC), 2,6-naphthalenedicarboxylic acid ligand (NDC). , 1,4-benzodiacetate ligand (PDA), 2,3-pyrazinedicarboxylic acid ligand (PZDC), 2,2-bis(4-carboxylphenyl)hexafluoropropane ligand (H2hfipbb), 1,4,5,8-naphthalenetetracarboxylic acid ligand (NTC), 5-tert-butyl-1,3-benzodicarboxylic acid ligand (TPIC), biphenyltetracarboxylic acid ligand (BPTC), 9,10-anthracenedicarboxylic acid ligand (ADC), 4-aminophenyltetrazolic acid ligand (APT), 2,4,6-pyridinetricarboxylic acid ligand (PYTA), 4,4',4' '-Benzene-1,3,5-triyltris-benzoic acid ligand (BTB), pyridinedicarboxylic acid ligand (PDC), 2,3-pyrazine-tetrazole ligand (DTP), glutaric acid ligand It may also include a child (GLA) and the like.

In one embodiment, the organic bridging ligand L may be selected from cyano groups, benzimidazole-based ligands and polycarboxylic acid-based ligands. In one embodiment, the organic bridging ligand L may be selected from cyano groups, benzimidazole-based ligands, trimesic acid-based ligands and terephthalic acid-based ligands. In one embodiment, the organic bridging ligand L includes a cyano group, a 5-chlorobenzimidazole ligand (cbIm), a trimesic acid ligand (BTC), a terephthalic acid ligand (BDC) and tris(2- benzimidazolemethyl)amine ligands (NTB).

Here, these polycarboxylic acid-based ligands in the present application are capable of coordinating with the central atom metal, leaving at least one hydrogen, and acting as Lewis bases in coordination compounds. is.

In formula (I), □ represents a ligand defect (ie, lattice vacancy). In the organic-inorganic hybrid type complexes of the present application, defects are due to the omission of the ligand alone or the simultaneous omission of the ligand and one or more metal or metal cluster atoms bound to it. Although the mechanism has not yet been fully elucidated, in the organic-inorganic hybrid complex of the present application, the defect present in the three-dimensional structure that is periodically assembled causes intermolecular hydrogen bonding with the solvent molecules of the electrolyte. It is possible to provide exposed sites for organic ligands with polar groups that can be formed. Therefore, when the organic-inorganic hybrid type complex of the present application is applied to the coating of the separator, it can improve the electrolytic solution wettability of the coated separator. Since the ligand defects are uniformly distributed in the organic-inorganic hybrid complex structure, the organic-inorganic hybrid complex of the present application effectively improves the electrolyte wettability of the separator and Liquid retention can be improved, which reduces the internal polarization of the battery cell, improves battery power density, and extends cycle life.

In formula (I), A represents an occludeable and releasable atom or cation. Optionally, A may be selected from atoms or cations of one or more of the metallic elements Li, Na, K, Rb, Cs, Sr, Zn, Mg and Ca. Further optionally, A represents Li or Na.

In formula (I), each numerical value among x, i, z, a and b is not limited. In one embodiment, x may take a number from 1 to 4. Further optionally, x may take a number from 1 to 3. In one embodiment, a may take a number greater than 0 and less than or equal to 4. Further optionally, a may take a number from 1 to 4. In one embodiment, b may take a number between 0 and 4 inclusive. Further optionally, b may take a number from 1 to 4. In one embodiment, z may take a number from 0 to 2. Further optionally, z may take a number from 0 to 1.

In formula (I), the relationship 0<i<x may be satisfied. In the corresponding defect-free organic-inorganic hybrid complex, i=0. The corresponding chemical formula is L _x [M _a C _b ]·A _z .

In this application, the value of i in formula (I) can be determined by the following method. Specifically, by known methods, for example, X-ray diffraction analysis (XRD), in situ cold field emission gun bispheric transmission electron microscopy (STEM), etc., the corresponding inorganic-organic hybrid complexes of the present application can be analyzed. A theoretical formula L _x [M _a C _b ]·A _z for the defective product can be determined. The above theoretical formula may be known to those skilled in the art. Also, based on the actually measured element ratios of the organic-inorganic hybrid type complex, the empirical formula L _x′ [M _a C _b ]·A _z of the basic unit in the complex can be obtained. The above elemental proportions can be determined by methods known in the art, such as inductively coupled plasma emission spectrum (ICP), carbon-sulfur elemental analyzer, elemental quantitative analysis (EA), and the like. Finally, obtaining the value of i by comparison between the empirical formula L _x′ [M _a C _b ]·A _z and the theoretical formula L _x [M _a C _b ]·A _z for the corresponding defect-free product. to determine the defect percentage i/x*100%, which represents the degree of defects of the organic-inorganic hybrid complex of the present application relative to an ideal defect-free crystal structure. Specifically, percent defect=(xx')/x*100%.

For illustrative purposes only, the determination of the corresponding defect-free theoretical formula will be described in more detail. Theoretically, when the types of all metal elements and ligands are clarified, the element ratio in the organic-inorganic hybrid type complex is determined by the valence of the metal element that accounts for the overwhelming proportion in the complex, and the corresponding depends only on the coordination number of the ligands involved. For example, there is only one type of M as a metal element in an organic-inorganic hybrid type complex. If the valence that accounts for the above ratio is +a ₁ and the coordination number of the ligand L is a ₂ , the theoretical chemical formula of the organic-inorganic hybrid type complex is L _a1 M _a2 if it does not form a metal cluster. There may be. If the organic-inorganic hybrid type complex does not participate in the construction of the molecular frame, that is, if there is an atom or cation A that can be occluded and released, and the valence of A is + _a3 , no metal cluster is formed, The theoretical chemical formula of the organic-inorganic hybrid complex may be L _a1 M _a2-a3/a1*z ·A _z . When forming metal clusters, the mode of existence of the metal clusters is investigated and the valence of the metal clusters is investigated by characterization means capable of analyzing the molecular structure, for example, in situ cold field emission gun bispheric transmission electron microscopy (STEM). You can substitute a number to trim. Finally, the theoretical formula L _x [M _a C _b ]·A _z of the defect-free product corresponding to the organic-inorganic hybrid complexes of the present application can be determined, where the subscripts a and b are It may be rounded to an integer if necessary.

In the organic-inorganic hybrid complexes of the present application, the defect percentage may be from about 1% to about 30%. The percent defect is optionally about 2% or more, further optionally about 3% or more, further optionally about 4% or more, further optionally about 5% or more. , further optionally greater than or equal to about 6%, further optionally greater than or equal to about 7%, and further optionally greater than or equal to about 8%. Also, said percent defect is optionally less than or equal to about 27.5%, further optionally less than or equal to about 25%, further optionally less than or equal to about 22.5%, further optionally 20% or less, further optionally about 17.5% or less, further optionally about 15% or less, further optionally about 12.5% or less, further optionally typically about 10% or less. In one embodiment, the defect percentage may be from about 2% to about 20%. In one embodiment, the defect percentage may be from about 5% to about 10%.

In formula (I), the relationship 1/2≤x:a≤3 may be satisfied. For clarity, x:a represents the ratio between ligands and defects and metal atoms. When M is a cation of more than one metal element, a represents the number of all metal cations in a single Formula I base unit.

In formula (I), the relationship 0≤b:a≤1 may be satisfied. When forming metal clusters M _a C _b , the ratio between a and b may satisfy 1/4≦b:a≦1.

In the organic-inorganic hybrid complexes of the present application, sufficient ligand defect sites (i.e., ligand exposed sites) are provided in the organic-inorganic hybrid complexes by applying the percent defects within the ranges described above. can provide. Although the mechanism has not yet been fully elucidated, when the organic-inorganic hybrid complex of the present application is applied to the coating of the separator for secondary batteries, the organic ligand polar group and the solvent molecule of the secondary battery electrolyte The formation of sufficient intermolecular hydrogen bonds between the The stability of the three-dimensional structure of the type complex is maintained, and it does not collapse during the charge/discharge process of the battery cell of the secondary battery. By applying the defect percentage within the range described above, it is possible to further suppress the occurrence of side reactions in the secondary battery and extend the cycle life of the battery cell.

In the present application, the defect formation may optionally be formed by adding an appropriate amount of a defect-introducing substance during the manufacturing process of the organic-inorganic hybrid complex. As non-limiting examples, the defect-introducing substance may be an acidic substance, an alkaline substance, a redox agent, a complexing agent, or the like. For example, in the process of synthesizing an organic-inorganic hybrid complex by a liquid phase coprecipitation method, in the process of dropping a salt solution containing a metal M into an acid, acid anhydride, or salt solution containing a corresponding ligand. , introduce defects into the organic-inorganic hybrid complex produced by adding appropriate amounts of other types of acids. By adjusting the percent defect of the organic-inorganic hybrid complex produced by varying the amount of added defect-introducing substances or other raw materials to bring the percent defect within the ranges defined in this application; The electrolyte wettability of the secondary battery separator can be sufficiently improved, the electrolyte retention rate can be improved, the polarization can be reduced, and the power density and cycle life of the battery can be improved.

In the organic-inorganic hybrid complexes of the present application, the basic units of formula (I) are assembled periodically along at least one of the three spatial directions X', Y' and Z' Preferably, said three directions X', Y' and Z' respectively form angles with the X, Y and Z directions of a Cartesian coordinate system between 0 and 75 degrees, optionally between 5 and 60 degrees. is the angle formed by In one embodiment, the basic units represented by formula (I) may be assembled periodically along at least one spatial direction of the X, Y and Z directions of a Cartesian coordinate system.

In the organic-inorganic hybrid complexes of the present application, the number of base units of formula (I) periodically assembled along at least one spatial direction may be from about 3 to about 10,000. .

On the other hand, the present application further provides a coating composition for use in secondary battery separators, which coating composition may comprise the organic-inorganic hybrid complex of the present application as described above.

The coating composition of the present application can be prepared by mixing the organic-inorganic hybrid complex of the present application with an adhesive by a suitable method.

In the coating composition of the present application, the content of the organic-inorganic hybrid complex may be from about 12 wt% to about 90 wt%, based on the total weight of the coating composition. Based on the total weight of the coating composition, the content of the organic-inorganic hybrid complex is optionally greater than or equal to about 17 wt%, further optionally greater than or equal to about 24 wt%, and further optionally about 27 wt% or greater, and optionally about 34 wt% or greater. and, based on the total weight of the coating composition, the content of the organic-inorganic hybrid complex is optionally less than or equal to about 90 wt%, more optionally less than or equal to about 85 wt%, and further optionally about 80 wt% or less, more optionally about 75 wt% or less, further optionally about 68 wt% or less. In one embodiment, the content of the organic-inorganic hybrid complex may be from about 17 wt% to about 85 wt%, based on the total weight of the coating composition. In one embodiment, the content of the organic-inorganic hybrid complex may be from about 34 wt% to about 68 wt%, based on the total weight of the coating composition.

Optionally, the coating composition of the present application may further comprise inorganic particles. For example, the inorganic particles may be selected from boehmite, zeolites, molecular sieves, alumina, aluminum oxyhydroxide, silicon dioxide, aluminum nitride, silicon carbide, magnesium oxide, calcium oxide, zinc oxide, zirconium oxide, titanium oxide and mixtures thereof. good. In such cases, the organic-inorganic hybrid complex and the inorganic particles can bind more tightly due to the complementarity between the particle morphologies, and the organic-inorganic hybrid complex improves the wetting property. Inorganic particles can provide a stiff and stable separator structure, and the two work synergistically.

When the coating composition of the present application contains inorganic particles, the mass ratio of the organic-inorganic hybrid complex to the total mass of the organic-inorganic hybrid complex and the inorganic particles in the coating composition is about 15 wt%. to about 85 wt%. The weight ratio of the organic-inorganic hybrid complex to the total weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be about 20 wt% or more, and optionally about 35 wt%. not less than, and optionally not less than about 40 wt%, and further optionally not less than about 55 wt%. And the weight ratio of the organic-inorganic hybrid complex to the total weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be up to about 80 wt%, optionally about 75 wt%. % or less, more optionally about 65 wt% or less, further optionally about 60 wt% or less. In one embodiment, the weight ratio of the organic-inorganic hybrid complex to the total weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be from about 20 wt% to about 80 wt%. In one embodiment, the weight ratio of the organic-inorganic hybrid complex to the combined weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be from about 40 wt% to about 80 wt%. In one embodiment, the weight ratio of the organic-inorganic hybrid complex to the combined weight of the organic-inorganic hybrid complex and the inorganic particles in the coating composition may be from about 40 wt% to about 60 wt%.

Optionally, the coating composition of the present application may further comprise one or more additives, such as adhesives, stabilizers, wetting agents, defoamers, rheology modifiers, pH adjusters. may be selected from one or more components of

As non-limiting examples, the adhesive in the coating composition can be acrylic acid, methyl acrylate, acrylic acid-acrylate-acrylonitrile polymers, or mixtures thereof.

As non-limiting examples, the stabilizer in the coating composition can be methylcellulose, hydroxyethylcellulose, sodium carboxymethylcellulose, or mixtures thereof.

As non-limiting examples, the wetting agent in the coating composition can be a polyoxyvinyl ether, a polyether silicone copolymer, a polyoxyethylene alkanolamide, or mixtures thereof.

As non-limiting examples, the defoamer in the coating composition can be polyoxypropylene glyceryl ether, polyoxyethyleneoxypropylene glyceryl ether, polydimethylsiloxane, or mixtures thereof.

As non-limiting examples, the rheology modifier in the coating composition can be ethanol, propylene glycol and propylene triol, or mixtures thereof.

As non-limiting examples, the pH modifier in the coating composition can be hydrochloric acid, sodium hydroxide, lithium hydroxide, sodium phosphate, sodium dihydrogen phosphate, lithium phosphate, lithium dihydrogen phosphate, or mixtures thereof. There may be.

On the other hand, the present application further provides a separator for secondary batteries. The secondary battery separator of the present application comprises a polymer substrate layer and a coating applied onto the substrate layer, wherein the coating comprises the organic-inorganic hybrid complex of the present application as described above or above. It may comprise the coating composition of the present application as described.

The present application further provides a secondary battery, which includes a positive electrode, a negative electrode, an electrolyte, and the above-described secondary battery separator of the present application.

The present application further provides a battery module, which includes the above-described secondary battery of the present application.

The present application further provides a battery pack, which includes the battery module of the present application as described above.

The present application further provides a power consuming device, which is a secondary battery of the present application as described above, or a battery module of the present application as described above, or a battery pack of the present application as described above, or a combination thereof including.

In the secondary battery of the present application, by applying the organic-inorganic hybrid type complex of the present application to the coating of the separator, the electrolyte wettability of the separator is significantly improved, and the electrolyte retention rate is greatly improved. This reduces the polarization and ultimately improves the power density and cycle life of the secondary battery significantly.

Hereinafter, the secondary battery, battery module, battery pack, and device of the present application will be described with reference to the drawings as appropriate.

In one embodiment of the present application, a secondary battery is provided.

A secondary battery typically includes a positive plate, a negative plate, an electrolyte, and a separator. During the charging and discharging process of the battery, active ions are intercalated and deintercalated between the positive and negative plates. The electrolyte serves to conduct ions between the positive and negative plates. The separator is placed between the positive electrode plate and the negative electrode plate, and mainly serves to prevent short-circuiting of the positive and negative electrodes, and allows ions to pass through.

[Positive plate]
The positive electrode plate includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material, the positive electrode active material including lithium cobaltate, Lithium nickel manganese cobalt oxide, lithium nickel manganese aluminate, lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium iron silicate, lithium vanadium silicate, lithium cobalt silicate, manganese silicate Including, but not limited to, lithium, spinel-type lithium manganate, spinel-type lithium nickel manganate, lithium titanate, and the like. One or more of these may be used for the positive electrode active material.

For example, the cathode current collector itself has two surfaces facing each other in the thickness direction, and the cathode film layer is placed on either one or both of the two facing surfaces of the cathode current collector. It is

In the secondary battery of the present application, the positive electrode current collector may employ a metal foil sheet or a composite current collector. For example, aluminum foil may be employed as the metal foil sheet. The composite current collector may include a polymeric material substrate and a metal layer formed on at least one surface of the polymeric material substrate. Composite current collectors combine metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) with polymeric material substrates (e.g., polypropylene (PP), polyethylene terephthalate (PET), substrates such as polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE)).

The positive electrode membrane layer optionally further comprises a conductive agent. However, the type of conductive agent is not specifically limited and can be selected by those skilled in the art according to actual needs. By way of example, the conductive agent used in the cathode film layer may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

In the present application, positive plates can be manufactured by methods known in the art. As an example, the cathode active material, conductive agent, and adhesive of the present application are dispersed in a solvent (eg, N-methylpyrrolidone (NMP)) to form a uniform cathode slurry, and the cathode slurry is coated on a cathode current collector. A positive electrode plate can be obtained through processes such as coating, drying, and cold pressing.

[Negative plate]
The negative plate includes a negative current collector and a negative film layer disposed on at least one surface of the negative current collector, and the negative film layer includes a negative active material.

In the secondary battery of the present application, the negative electrode active material for manufacturing a secondary battery negative electrode, which is commonly used in the art, can be used as the negative electrode active material, including artificial graphite and natural graphite. , soft carbon, hard carbon, silicon-based materials, tin-based materials and lithium titanate. The silicon-based material may be selected from one or more of elemental silicon, silicon oxides (eg, silicon suboxides), silicon-carbon composites, silicon-nitrogen composites, and silicon alloys. The tin-based material may be selected from one or more of elemental tin, tin oxide, and tin alloys.

For example, the negative electrode current collector itself has two surfaces facing each other in the thickness direction, and the negative electrode film layer is disposed on either one or both of the two facing surfaces of the negative electrode current collector. It is

In the secondary battery of the present application, the negative electrode current collector may employ a metal foil sheet or a composite current collector. For example, a copper foil may be employed as the metal foil sheet. The composite current collector may include a polymeric material substrate and a metal layer formed on at least one surface of the polymeric material substrate. Composite current collectors combine metal materials (copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) with polymeric material substrates (e.g., polypropylene (PP), polyethylene terephthalate (PET), substrates such as polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE)).

In the secondary battery of the present application, the negative electrode film layer usually contains a negative electrode active material, an optional adhesive, an optional conductive agent, and other optional auxiliary agents, and usually contains a negative electrode slurry. Formed by coating and drying. The negative electrode slurry is generally formed by dispersing a negative electrode active material, a selective conductive agent, an adhesive, etc. in a solvent and stirring uniformly. The solvent may be N-methylpyrrolidone (NMP) or deionized water.

By way of example, the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.

Examples of adhesives include styrene butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA) and carboxymethylchitosan (CMCS).

Other optional auxiliaries are, for example, thickening agents such as sodium carboxymethylcellulose (CMC-Na).

In some embodiments, the positive plate, negative plate and separator can be manufactured into an electrode assembly by a winding process or a lamination process.

[Electrolytes]
The embodiments of the present application are not specifically limited to the type of electrolyte, and can be selected according to demand. For example, the electrolyte may be solid or liquid.

In some embodiments, the electrolyte is liquid and typically includes an electrolyte salt and a solvent.

Exemplary electrolytes include lithium hexafluorophosphate ( _LiPF6 ), lithium tetrafluoroborate ( _LiBF4 ), lithium perchlorate ( _LiClO4 ), lithium hexafluoroarsenate ( _LiAsF6 ), lithium bisfluorosulfonimide. (LiFSI), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluoro(oxalato)borate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium difluorophosphate ( _LiPO2 ) F ₂ ), lithium difluoro(oxalato)borate (LiDFOP) and lithium tetrafluoro(oxalato)phosphate (LiTFOP).

Examples of solvents include fluoroethylene carbonate (FEC), ethylene carbonate (EC), propylene carbonate (PC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), diphenyl carbonate (DPC), Methyl propyl carbonate (MPC), Ethyl propyl carbonate (EPC), Fluoroethylene carbonate (BC), Methyl formate (MF), Methyl acetate (MA), Ethyl formate (EA), Propyl acetate (PA), Methyl propionate (MP ), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethylsulfone (MSM), methyl ethyl It may be selected from one or more of sulfone (EMS) and diethylsulfone (ESE).

In some embodiments, the electrolyte further optionally comprises additives. For example, the electrolyte may include a negative electrode film-forming additive, a positive electrode film-forming additive, an additive that improves the overcharge performance of the battery, an additive that improves the high temperature performance of the battery, and an additive that improves the low temperature performance of the battery. It may also contain agents and the like.

[Separator]
The separator separates the positive and negative plates, prevents short circuits inside the battery, and allows active ions to migrate between the positive and negative electrodes through the separator. In the secondary battery of the present application, the separator for the secondary battery of the present application described above including the polymer base layer and the coating applied on the base layer is used as the separator that performs the above function. In said separator, the coating may comprise the organic-inorganic hybrid complex of the present application as described above or the coating composition of the present application as described above.

The present application does not specifically limit the type of polymer substrate layer and any known polymer substrate layer with good chemical and mechanical stability can be used. In some embodiments, any known porous structure film used in secondary batteries can be used as the base layer of the secondary battery separator of the present application. For example, the substrate layer may be a glass fiber thin film, a nonwoven fabric thin film, a polyethylene (PE) thin film, a polypropylene (PP) thin film, a polyvinylidene fluoride thin film, and a multilayer composite thin film including one or more of them. One or more may be selected. In some embodiments, polyolefin microporous membranes common in the art can be used as the base layer of the secondary battery separator of the present application. As non-limiting examples, the polyolefin microporous membrane may be a polyethylene (PE) monolayer membrane, a polypropylene (PP) monolayer membrane, and a PP/PE composite PP/PE/PP multi-layer microporous membrane. For example, a PP-PE polymer microporous thin film with a thickness of about 20 μm and an average pore size of about 80 nm can be used as the base layer of the secondary battery separator of the present application.

The coating applied onto the substrate layer can be formed by applying the organic-inorganic hybrid complex of the present application or the coating composition of the present application to the polymeric substrate layer by methods common in the art. can. For example, a slurry containing the organic-inorganic hybrid complex of the present application or the coating composition of the present application is applied to at least one surface of a substrate layer of a secondary battery separator by a general coating method such as a scratch coating method. to form a wet coating on the surface. The solids content of the slurry may be from about 5% to about 10%, such as about 9%. After drying the wet coating, a coating is formed on at least one surface of the separator. The thickness of the coating may be about 1-8 μm, eg about 5 μm.

In some embodiments, the secondary battery may be a lithium ion secondary battery.

In some embodiments, the positive plate, negative plate and separator can be manufactured into an electrode assembly by a winding process or a lamination process.

In some embodiments, a secondary battery may include a sheath. This outer packaging may be used to package the electrode assembly and electrolyte solution described above.

In some embodiments, the secondary battery housing may be a hard case, such as a hard plastic case, an aluminum case, a steel case, and the like. The packaging of the secondary battery may be a soft bag, for example, a bag-type soft bag. The material of the pouch may be plastic, and examples of plastic include polypropylene (PP), polybutylene terephthalate (PBT), polybutylene succinate (PBS), and the like.

The present application does not specifically limit the shape of the secondary battery, which may be cylindrical, square or any other shape. For example, FIG. 1 shows a secondary battery 5 having a square structure as an example.

In some embodiments, referring to FIG. 2, the exterior may include a case 51 and a lid plate 53. As shown in FIG. Here, the case 51 may include a bottom plate and side plates connected on the bottom plate, the bottom plate and the side plates enclosing to form a receiving chamber. The case 51 has an opening that communicates with the storage chamber, and the cover plate 53 can cover the opening to block the storage chamber. The positive plate, negative plate and separator can form the electrode assembly 52 by a winding process or a lamination process. The electrode assembly 52 is packaged within the housing. Electrolyte solution is infiltrated into the electrode assembly 52 . The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and can be selected by those skilled in the art according to specific actual needs.

In some embodiments, the secondary battery can be assembled into a battery module, and the number of secondary batteries included in the battery module can be one or more, and the specific number can be determined by those skilled in the art. Selection can be made based on the application and capacity of the battery module.

FIG. 3 shows a battery module 4 as an example. Referring to FIG. 3 , in battery module 4 , a plurality of secondary batteries 5 may be arranged and installed sequentially along the longitudinal direction of battery module 4 . Of course, any other arrangement may be used. Further, the plurality of secondary batteries 5 may be fixed by fasteners.

Optionally, the battery module 4 may further include a housing having an accommodation space, and the plurality of secondary batteries 5 are accommodated in this accommodation space.

In some embodiments, the battery modules can be further assembled into a battery pack, and the number of battery modules included in the battery pack can be selected by those skilled in the art based on the application and capacity of the battery pack.

4 and 5 show the battery pack 1 as an example. 4 and 5, the battery pack 1 may include a battery box and a plurality of battery modules 4 installed within the battery box. The battery box includes an upper housing 2 and a lower housing 3 , the upper housing 2 shielding the lower housing 3 and capable of forming an enclosed space for housing the battery modules 4 . A plurality of battery modules 4 may be arranged in the battery box in any manner.

Also, the present application further provides an apparatus, the apparatus including one or more of a secondary battery, battery module or battery pack according to the present application. A secondary battery, battery module or battery pack may be used as the device's power source or may be used as the device's energy storage unit. Devices include mobile devices (e.g., mobile phones, laptops, etc.), electric vehicles (e.g., pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), It may be, but is not limited to, trains, ships and satellites, energy storage systems, and the like.

A secondary battery, a battery module, or a battery pack can be selected as the power consumption device according to the demand for its use.

FIG. 6 is an example power consumption device. The device may be a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle. Battery packs or battery modules may be employed for this power consuming device to meet the high power and high energy density demands for secondary batteries.

Another example power consuming device may be a mobile phone, a tablet computer, a laptop, or the like. This device is usually required to be lightweight and thin, and can employ a secondary battery as a power source.

The above inventive content of the present application is not intended to describe each disclosed embodiment or each implementation of the present application. The description that follows more particularly exemplifies illustrative embodiments. In multiple places throughout this application, guidance is provided through a series of embodiments that can be used in various combinations. In each example, only representative groups are listed and should not be construed as exhaustive.

In the following production examples, examples and application examples, if specific conditions are not specified, it means that the described steps are performed according to general conditions or conditions suggested by the manufacturer. All reagents or instruments used are commercially available and common products unless the manufacturer is specified.

Preparation of Organic-Inorganic Hybrid Complex In summary, the organic-inorganic hybrid complex compound of the present application can be prepared by a liquid-phase coprecipitation method. An acid, acid anhydride or salt containing the corresponding ligand L and a salt containing the corresponding metal M or metal cluster M _a C _b are added in a polar solvent such as water or aqueous ammonia, ethanol, methanol, DMF. Stir and mix in, react at a temperature from room temperature to 150° C., and add a substance that introduces defects, such as an acidic substance, an alkaline substance, a redox agent, and the like. After the reaction is complete, the reaction mixture is aged for about 1-48 hours. The solid product is then recovered by suction filtration. The recovered solid product is activated at a temperature of about 140° C. to about 160° C. for about 8-12 hours to obtain the final organic-inorganic hybrid complex product.

Production example 1
Equimolar FeCl ₂ (127 g) and Na ₄ Fe(CN) ₆ (304 g) are weighed as raw materials. The two raw materials are respectively added to 10 L of deionized water to prepare 0.1M _FeCl2 solution and 0.1M _Na4Fe (CN) ₆ solution. The two solutions are each heated to about 80° C. and maintained at this temperature. The FeCl ₂ solution is dropped into the Na ₄ Fe(CN) ₆ solution at a rate of about 1 mL/min to cause a coprecipitation reaction to obtain a precipitate. Ligand defects are introduced by injecting dilute hydrochloric acid (3.5 g in pure HCl equivalent mass) as an acidic substance at one time during the dropping process. After the reaction is complete, the reaction mixture is aged at about 80° C. for about 24 hours. The solid product is then recovered by suction filtration. The recovered solid product is then activated at a temperature of about 150°C for about 10 hours. Finally, 133 g of solid product are obtained.

The resulting solid product is characterized to determine the chemical formulas of the basic units of the final organic-inorganic hybrid complex compound. Specifically, the obtained solid product is vacuum-dried at 150° C. as a specimen to remove adsorbed moisture impurities. The sample is then subjected to an ICP test (SPECTRO BLUE, from SPECTRO Analytical Instruments GmbH) to determine the Fe and Na contents to be 37.76% and 11.97%, respectively. In addition, a carbon sulfur test (carbon sulfur analyzer, CS844, from LECO Corporation) and an elemental analysis test (Vario EL III, from Elemental Analysensysteme GmbH) showed that the content of C and N was 22.93%, respectively. 26.75%. The above tests determine the product's empirical formula to be (CN) _2.79 Fe.Na _0.76 . The theoretical formula for the corresponding defect-free product is (CN) ₃ Fe· Na. From the above results, the organic-inorganic hybrid complex actually obtained in this production example was found to have a basic unit represented by [(CN) _2.79 □ _0.21 ]Fe·Na _0.76 . Do you get it. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Scanning electron microscopy (SEM) characterization (Sigma 300 from Carl-Zeiss Jena GmbH) is performed on the resulting organic-inorganic hybrid complex material. The SEM photograph obtained is shown in FIG.

Production example 2
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, with the only difference being that the mass of dilute hydrochloric acid added in the production process was 0.6 g in terms of pure HCl. Finally, 141 g of solid product are obtained.

By the same characterization method as in Production Example 1, the organic-inorganic hybrid complex produced in this Production Example has a basic unit represented by [(CN) _2.97 □ _0.03 ]Fe·Na _0.95 . Then decide. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 1.0%.

Production example 3
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, the only difference being that the mass of diluted hydrochloric acid added in the production process was 2.8 g in terms of pure HCl. Finally, 139 g of solid product are obtained.

By the same characterization method as in Preparation Example 1, the organic-inorganic hybrid complex prepared in this example has a basic unit represented by [(CN) _2.925 □ _0.075 ]Fe·Na _0.90 . Then decide. In the organic-inorganic hybrid complex produced in this example, the defect percentage is 2.5%.

Production example 4
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, with the only difference being that the mass of dilute hydrochloric acid added in the production process was 9.7 g in terms of pure HCl. Finally, 118 g of solid product are obtained.

By the same characterization method as in Preparation Example 1, the organic-inorganic hybrid complex prepared in this example has a basic unit represented by [(CN) _2.46 □ _0.54 ]Fe·Na _0.42 . Then decide. In the organic-inorganic hybrid complex produced in this example, the defect percentage is 18.0%.

Production example 5
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, with the only difference being that the mass of dilute hydrochloric acid added in the production process was 13.2 g in terms of pure HCl. Finally, 108 g of solid product are obtained.

By the same characterization method as in Production Example 1, the organic-inorganic hybrid complex produced in this example has a basic unit represented by [(CN) _2.25 □ _0.75 ]Fe·Na _0.2 . Then decide. In the organic-inorganic hybrid complex produced in this example, the defect percentage is 25.0%.

Production example 6
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, except that the 0.1 M FeCl ₂ solution and the 0.1 M Na ₄ Fe(CN) ₆ solution in Production Example 1 were replaced with , prepare 0.1M _MnCl2 solution and 0.1M _Na4Mn (CN) ₆ solution in 10 L deionized water respectively to carry out the co-precipitation reaction, without adding dilute hydrochloric acid in the production process, _O2 It is only possible to introduce ligand defects by continuously flowing . The _O2 flux is 1.7*total solution volume/hour. Finally, 132 g of solid product are obtained.

By a test method analogous to Preparation 1, the empirical formula of the product is determined to be (CN) _2.79 Mn.Na _0.76 . Also, by a method similar to Production Example 1, the theoretical formula of the corresponding defect-free product was determined as (CN) ₃ Mn·Na. From the above results, the organic-inorganic hybrid complex actually obtained in this production example was found to have a basic unit represented by [(CN) _2.79 □ _0.21 ]Mn·Na _0.76 . Do you get it. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Production example 7
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 6, except that the 0.1 M MnCl ₂ solution and the 0.1 M Na ₄ Mn(CN) ₆ solution in Production Example 6 were replaced with , prepare 0.1 M _CoCl2 solution and 0.1 M _Na4Co (CN) ₆ solution in 10 L of deionized water respectively to carry out the co-precipitation reaction. Finally, 136 g of solid product are obtained.

By a test method analogous to Preparation 1, the empirical formula of the product is determined to be (CN) _2.79 Co.Na _0.76 . Also, by a method similar to Production Example 1, the theoretical formula of the corresponding defect-free product was determined as (CN) ₃ Co·Na. From the above results, the organic-inorganic hybrid complex actually obtained in this production example was found to have a basic unit represented by [(CN) _2.79 □ _0.21 ]Co·Na _0.76 . Do you get it. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Production example 8
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 6, except that the 0.1 M MnCl ₂ solution and the 0.1 M Na ₄ Mn(CN) ₆ solution in Example 6 were replaced with , prepare a 0.1 M _MnCl2 solution and a 0.1 M _Na4Fe (CN) ₆ solution in 10 L of deionized water respectively to carry out the co-precipitation reaction. Finally, 136 g of solid product are obtained.

By a test method analogous to Preparation 1, the empirical formula of the product is determined to be (CN) _2.79 [Fe _0.5 Mn _0.5 ]·Na _0.76 . Also, by a method similar to Production Example 1, the theoretical formula of the corresponding defect-free product was determined as (CN) ₃ [Fe _0.5 Mn _0.5 ]·Na. From the above results, the organic-inorganic hybrid type complex actually obtained in this production example is [(CN) _2.79 □ _0.21 ][Fe _0.5 Mn _0.5 ]·Na _0.76. It was found to have a base unit expressed as In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Production example 9
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, except that Co(NO ₃ ) ₂ and 5-chlorobenzimidazole were used as raw materials and used in Production Example 1. Instead of deionized water, 10 L of mixed solvent of _H2O and DMF (1:1) was used instead of 0.1M _FeCl2 solution and 0.1M _Na4Fe (CN) ₆ solution in Preparation Example 1. 2, 0.1M Co(NO ₃ ) ₂ solution and 0.2M 5-chlorobenzimidazole solution were prepared respectively, and the coprecipitation reaction was carried out. It only introduces ligand defects by adding some NaOH. Finally, 293 g of solid product are obtained.

A test method similar to that of Preparation 1 determines the empirical formula of the product to be (cbIm) _1.86 Co. Also, by a method similar to Preparation Example 1, the theoretical formula of the corresponding defect-free product was determined as (cbIm) ₂ Co. From the above results, it was found that the organic-inorganic hybrid complex actually obtained in this production example has a basic unit represented by [(cbIm) _1.86 □ _0.14 ]Co. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Production example 10
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 9, the only difference being that the mass of NaOH added during the production process was 0.6 g. Finally, 309 g of solid product are obtained.

A characterization method similar to that of Preparation 9 determines that the hybrid organic-inorganic complex prepared in this preparation has a base unit represented by [(cbIm) _1.98 □ _0.02 ]Co. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 1.0%.

Production Example 11
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 9, the only difference being that the mass of NaOH added during the production process was 1.2 g. Finally, 305 g of solid product are obtained.

A characterization method similar to that of Preparation 9 determines that the hybrid organic-inorganic complex prepared in this preparation has a base unit represented by [(cbIm) _1.95 □ _0.05 ]Co. The defect percentage is 2.5% in the organic-inorganic hybrid complex produced in this preparation example.

Production example 12
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 9, the only difference being that the mass of NaOH added during the production process was 4.5 g. Finally, 265 g of solid product are obtained.

A characterization method similar to that of Preparation 9 determines that the hybrid organic-inorganic complex prepared in this preparation has a base unit represented by [(cbIm) _1.64 □ _0.36 ]Co. The defect percentage is 18% in the organic-inorganic hybrid complex produced in this preparation example.

Production example 13
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 9, the only difference being that the mass of NaOH added during the production process was 8.4 g. Finally, 246 g of solid product are obtained.

A characterization method similar to that of Preparation 9 determines that the hybrid organic-inorganic complex prepared in this preparation has a base unit represented by [(cbIm) _1.50 □ _0.50 ]Co. The defect percentage is 25% in the organic-inorganic hybrid complex produced in this preparation example.

Production example 14
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, except that the raw materials used were trimesic acid tripotassium salt, trimesic acid, and Cu(NO ₃ ) ₂ . Instead of the deionized water used in 1, 10 L of a mixed solvent of H ₂ O and EtOH (1:1) was used, and The Cu(NO ₃ ) ₂ solutions are prepared one by one and mixed one by one. Finally, 758 g of solid product are obtained.

By a test method analogous to Preparation 1, the empirical formula of the product is determined to be (BTC) _1.86 Cu ₃ ·K. Also, by a method similar to Preparation Example 1, the theoretical formula of the corresponding defect-free product was determined as (BTC) ₂ Cu ₃ ·K. From the above results, it was found that the organic-inorganic hybrid type complex actually obtained in this production example has a basic unit represented by [(BTC) _1.86 □ _0.14 ]Cu ₃ ·K. . In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Production example 15
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, except that the raw materials used were monolithium terephthalate, terephthalic acid, Fe(ClO ₄ ) ₃ and HF, and Instead of the deionized water used in Production Example 1, 10 L of a mixed solvent of H ₂ O and EtOH (1:1) was used, and 0.05 M monolithium terephthalate solution, 0.05 M terephthalic acid solution A 1 M Fe(ClO ₄ ) ₃ solution and a 0.02 M HF solution are prepared in sequence and mixed one by one into the solution, and the mass of dilute hydrochloric acid added in the manufacturing process is 3.7 g in terms of pure HCl. Only. Finally, 188 g of solid product are obtained.

By a test method analogous to Preparation 1, the empirical formula of the product is determined to be (BDC) _0.93 [Fe(OH) _0.8 F _0.2 ]·Li _0.5 . Also, by a method similar to Preparation Example 1, the theoretical formula of the corresponding defect-free product was determined as (BDC)[Fe(OH) _0.8 F _0.2 ]·Li _0.5 . From the above results, the organic-inorganic hybrid type complex actually obtained in this production example is [(BDC) _0.93 □ _0.07 ][Fe(OH) _0.8 F _0.2 ]·Li _0. It was found to have a basic unit represented by ₅ . In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Production example 16
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, except that the raw materials used were magnesium tris(2-benzimidazolemethyl)amine (Mg ₃ (NTB) ₂ ), tris ( 2-benzimidazolemethyl)amine and Zn(NO ₃ ) ₂ , and instead of the deionized water used in Production Example 1, 10 L of a mixed solvent of H ₂ O and EtOH (1:1) was used, .002M magnesium tris(2-benzimidazolemethyl)amine (Mg ₃ (NTB) ₂ ) solution, 0.112M tris(2-benzimidazolemethyl)amine solution, and 0.24M Zn(NO ₃ ) ₂ solution were prepared in sequence. and mixed one by one, and the mass of diluted hydrochloric acid added in the manufacturing process is 3.7 g in terms of pure HCl. Finally, 519 g of solid product are obtained.

By a test method analogous to Preparation 1, the empirical formula of the product is determined to be (NTB) _1.86 [Zn ₄ O].Mg _0.1 . Also, by a method similar to Preparation Example 1, the theoretical formula of the corresponding defect-free product was determined as (NTB) ₂ [Zn ₄ O]·Mg _0.1 . From the above results, the organic-inorganic hybrid type complex actually obtained in this production example has a basic unit represented by [(NTB) _1.86 □ _0.14 ][Zn ₄ O]·Mg _0.1 . found to have. In the organic-inorganic hybrid complex produced in this production example, the defect percentage is 7.0%.

Comparative production example 1
A defect-free organic-inorganic hybrid complex (CN) ₃ Fe·Na is produced according to a general method. Specifically, equimolar amounts of FeCl ₂ (127 g) and Na ₄ Fe(CN) ₆ (304 g) are weighed as raw materials. The two raw materials are respectively added to 10 L of deionized water to prepare 0.1M _FeCl2 solution and 0.1M _Na4Fe (CN) ₆ solution. The two solutions are each heated to about 80° C. and maintained at this temperature. The FeCl ₂ solution is dropped into the Na ₄ Fe(CN) ₆ solution at a rate of about 1 mL/min to cause a coprecipitation reaction to obtain a precipitate. After the reaction is complete, the reaction mixture is aged at about 80° C. for about 24 hours. The solid product is then recovered by suction filtration. The recovered solid product is then activated at a temperature of about 150°C for about 10 hours. Finally, 146 g of solid product are obtained.

The organic-inorganic hybrid complex prepared in this comparative preparation example is defect-free, ie, the defect percentage is zero.

Comparative production example 2
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, with the only difference being that the mass of dilute hydrochloric acid added in the production process was 0.3 g in terms of pure HCl. Finally, 145 g of solid product are obtained.

By the same characterization method as in Production Example 1, the organic-inorganic hybrid complex produced in this Production Example has a basic unit represented by [(CN) _2.985 □ _0.015 ]Fe·Na _0.99 . Then decide. In the organic-inorganic hybrid complex produced in this comparative production example, the defect percentage is 0.5%.

Comparative production example 3
An organic-inorganic hybrid complex was produced by basically the same production method as in Production Example 1, the only difference being that the mass of diluted hydrochloric acid added in the production process was 23.1 g in terms of pure HCl. Finally, 97 g of solid product are obtained.

By the same characterization method as in Production Example 1, the organic-inorganic hybrid complex produced in this Production Example has a basic unit represented by [(CN) _1.8 □ _1.2 ]Fe·Na _0.1 . Then decide. In the organic-inorganic hybrid complex produced in this comparative production example, the defect percentage is 40.0%.

Comparative production example 4
A defect-free organic-inorganic hybrid type complex (cbIm) ₂ Co was produced according to a general production method basically in the same manner as in Comparative Production Example 1, except that the raw material used was Co(NO ₃ ) _{2 .} and 5-chlorobenzimidazole, and instead of the deionized water used in Comparative Production Example 1, 10 L of a mixed solvent of H ₂ O and DMF (1:1) was used. Instead of 1 M _FeCl2 solution and 0.1 M _Na4Fe (CN) ₆ solution, 0.1 M Co( _NO3 ) ₂ solution and 0.2 M 5-chlorobenzimidazole solution were prepared, respectively, for the coprecipitation reaction. is to use. Finally, 326 g of solid product are obtained.

The organic-inorganic hybrid complex prepared in this comparative preparation example is defect-free, ie, the defect percentage is zero.

Comparative production example 5
A defect-free organic-inorganic hybrid complex (BTC) ₂ Cu ₃ ·K was produced according to a general production method by basically the same method as in Comparative Production Example 1, the difference being that the raw material used was trimesic acid. Potassium salt, trimesic acid and Cu(NO ₃ ) ₂ , and instead of the deionized water used in Preparation Example 1, 10 L of a mixed solvent of H ₂ O and EtOH (1:1) was used; 05M trimesic acid tripotassium salt solution, 0.25M trimesic acid solution and 0.45M Cu(NO ₃ ) ₂ solution are prepared in sequence and mixed one by one. Finally, 832 g of solid product are obtained.

The organic-inorganic hybrid complex prepared in this comparative preparation example is defect-free, ie, the defect percentage is zero.

Comparative production example 6
A defect-free organic-inorganic hybrid type complex (BDC) [Fe(OH) _0.8 F _0.2 ]·Li _0.5 was produced according to a general production method by basically the same method as in Comparative Production Example 1. However, the difference is that the raw materials used are monolithium terephthalate, terephthalic acid, Fe(ClO ₄ ) ₃ and HF, and H ₂ O and EtOH are used instead of the deionized water used in Preparation Example 1. 0.05M monolithium terephthalate solution, 0.05M terephthalic acid solution, 0.1M Fe(ClO ₄ ) ₃ solution and 0.02M HF solution were prepared in sequence using 10 L of a mixed solvent (1:1) of and only one by one mixed into the solution. Finally, 205 g of solid product are obtained.

The organic-inorganic hybrid complex prepared in this comparative preparation example is defect-free, ie, the defect percentage is zero.

Comparative Production Example 7
A defect-free organic-inorganic hybrid complex (NTB) ₂ [Zn ₄ O]·Mg _0.1 was produced according to a general production method by basically the same method as in Comparative Production Example 1, and the difference was that The starting materials are magnesium tris(2-benzimidazolemethyl)amine (Mg ₃ (NTB) ₂ ), tris(2-benzimidazolemethyl)amine and Zn(NO ₃ ) ₂ , and the deionized water used in Production Example 1 10 L of a mixed solvent of H ₂ O and EtOH (1:1) was used instead of 0.002 M magnesium tris(2-benzimidazolemethyl)amine (Mg ₃ (NTB) ₂ ) solution, 0.112 M Tris (2-Benzimidazolemethyl)amine solution and 0.24M Zn(NO ₃ ) ₂ solution are prepared one by one and mixed one by one. Finally, 567 g of solid product are obtained.

The organic-inorganic hybrid complex prepared in this comparative preparation example is defect-free, ie, the defect percentage is zero.

Separator Production Example 1
A commercially available PP-PE polymer microporous thin film with a thickness of 20 μm and an average pore size of 80 nm (model number 20 from Shukutaka Electronics Co., Ltd.) is used as the substrate layer. Using the organic-inorganic hybrid type composite compound produced in Production Example 1 above as a raw material, a commercially available adhesive, polymethyl acrylate (CAS: 9003-21-8, from Hubei Nono Co., Ltd.), is commercially available. acrylic acid-acrylic acid ester-acrylonitrile polymer (from Hubei Nuona Co., Ltd., CAS: 25686-45-7), commercial stabilizer sodium carboxymethylcellulose (chemically pure, Shanghai Chang Guang Enterprise CAS: 9004-32-4 from Development Co., Ltd.), a commercial wetting agent polyoxyvinyl ether (CAS: 27252-80-8 from Hubei Nuona Co., Ltd.) and 85:6:3:3:3 Mix uniformly in mass ratio. Mix and add water to form a slurry with a solids content of about 9%. The slurry is applied to the two surfaces of the substrate layer by a scratch coating method to form a wet coating having a thickness of about 30 μm on each of the two surfaces. The substrate layer with the wet coating is transferred to the open and dried at a temperature of about 80° C. for about 60 minutes to obtain a separator with a coating thickness of about 5 μm.

Scanning electron microscopy (SEM) characterization (Sigma 300, from Carl-Zeiss Jena GmbH) is performed on the separator with the resulting coating. The SEM picture obtained is shown in FIG.

Examples 2-16 and Comparative Examples 1-7
Separators were produced in Examples 2 to 16 and Comparative Examples 1 to 7 by basically the same method as in Example 1, except that the organic-inorganic hybrid type composite compound used in Example 1 was replaced with The organic-inorganic hybrid composite compounds prepared in Examples 2-16 and Comparative Preparation Examples 1-7 are only used.

Example 17
A coated separator is manufactured by basically the same method as in Example 1, except that commercial alumina (from Shandong Shuchuan Chemical Technology Co., Ltd.) is used instead of a certain weight ratio of organic-inorganic hybrid type composite compound. is used, and the weight ratio of the organic-inorganic hybrid type composite compound and alumina is set to 4:1.

Examples 18-20
Separators were produced in Examples 18 to 20 by basically the same method as in Example 17, except that in Examples 18 to 20, the weight ratio of the organic-inorganic hybrid type composite compound and alumina was 3:2. , 2:3 and 1:4.

Control example 1
A commercially available PP-PE polymer microporous thin film (from Shukutaka Electronic Technology Co., Ltd.) with a thickness of 20 μm and an average pore size of 80 nm is used directly as a separator (PP-PE bare film).

Control example 2
A separator was manufactured by basically the same method as in Example 1, the only difference being that the organic-inorganic hybrid type composite compound used in Example 1 was all replaced with alumina of the same weight.

Battery cell manufacturing application example 1
Na _0.9 Fe _0.5 Mn _0.5 O ₂ as an active material, acetylene black (Denka Black, from Nippon Denka Co., Ltd.) as a conductive agent, and polyvinylidene fluoride (HSV 900, from Arkema Group) as an adhesive. ) in a weight ratio of 94:3:3 in the N-methylpyrrolidone solvent system with sufficient agitation to mix homogeneously to obtain a slurry with a solids content of 30%. This slurry is used to form a wet coating with a thickness of 250 μm on one side of an Al foil with a thickness of 12 μm by a transfer coating method. Then, the Al foil with the wet coating is transferred to an open, dried at a temperature of 150° C. for 60 minutes, and cold-pressed with a roll press at a pressure of 60 tons to obtain a positive electrode plate, where , the dry coating thickness on one side of the Al foil is 130 μm.

Hard carbon as an active material, acetylene black as a conductive agent, styrene-butadiene rubber as an adhesive, and carboxymethyl cellulose sodium as a thickener were mixed in a deionized water solvent at a weight ratio of 95:2:2:1. Stir well to mix evenly and obtain a slurry with a solids content of 15%. The slurry is applied to one side of an Al foil with a thickness of 12 μm by a doctor blade method to form a wet coating with a thickness of 120 μm. Then, the Al foil with the wet coating is transferred to an open, dried at a temperature of 150° C. for 60 minutes, and cold-pressed at a pressure of 50 tons using a cold-press machine to obtain a negative electrode plate, Here, the dry coating thickness on the Al foil is 60 μm.

The positive electrode plate, the separator obtained in Example 1, and the negative electrode plate are sequentially wound to form a bare battery cell having a winding laminate structure with dimensions of 16 cm×10 cm×2.8 cm. This pair of battery cells is put into a steel case, filled with 150 g of electrolyte and packaged to obtain a battery cell. The electrolyte is a propylene carbonate solution with a composition of 1M _NaPF6 .

Application Examples 2-20, Comparative Application Examples 1-7 and Control Application Examples 1 and 2
Battery cells were manufactured in Application Examples 2-20, Comparative Application Examples 1-7 and Control Application Examples 1 and 2 by essentially the same method as in Application Example 1, the difference being that the separator used in Application Example 1 was replaced. In addition, the separators in Examples 2-20, Comparative Examples 1-7 and Control Examples 1 and 2 are used, respectively.

Performance Tests Separators and Application Examples 1-20, Comparative Applications 1-7 and Control Applications 1 and 2 prepared in Examples 1-20, Comparative Examples 1-7 and Control Examples 1 and 2 were tested according to the following performance tests. Evaluate the battery cells manufactured in

Test example 1
In this test example, the electrolyte wettability of each separator is evaluated. Specifically, one drop (about 0.05 mL) of a proton-type hydrophilic electrolyte solution (1M NaPF ₆ ethylene carbonate (EC): methyl ethyl carbonate (EMC) = 1/1 W/W solution) was placed horizontally. drip onto the separator placed in the After 5 minutes, the approximate area of electrolyte infiltration is statistically determined by the grid method. Specifically, the measurement method of the grid method is as follows. After 5 minutes, the upper surface of the separator was photographed from directly above, and the entire area where the traces of electrolyte infiltration appeared in the photograph was covered with a grid with an area of 0.01 cm ² , and the traces of electrolyte infiltration were completely occupied in the image. A grid is described as "completely infiltrated", a grid with an electrolyte solution infiltration area of more than half is also described as "completely infiltrated", and a grid with an electrolyte solution infiltration of less than half is described as "not infiltrated". Finally, the electrolyte wettability of the separator is equal to the number of fully wetted grids times 0.01, expressed in units of cm ² .

As an example, when the separators of Control Example 1, Comparative Example 1 and Example 1 were subjected to the electrolyte wettability test, the photographs obtained are shown in FIGS. 9a, 9b and 9c, respectively. In Figures 9a, 9b and 9c, the numbers of "completely wetted" grids are 43, 272 and 400, respectively, so that the electrolyte wettability of the separators of Control 1, Comparative Example 1 and Example 1 is 0.43 cm, respectively. ² , 2.72 cm ² and 4.00 cm ² .

Test example 2
In this test example, the electrolytic solution retention rate of each separator is evaluated. Specifically, a separator having dimensions of 10 cm x 10 cm x 25 µm (the thickness of the separator is 20 µm because no coating is formed on the surface of the separator of Control Example 1) is taken, and the dry weight of this separator, _W0, is Weigh. After immersing the separator in the electrolytic solution for 10 hours, the separator is allowed to stand still in a closed container for 1 hour to saturate the electrolytic solution in the separator, and the wet weight W of the separator is weighed. The electrolyte retention rate is calculated based on the following formula.

Electrolyte retention rate = [(WW ₀ )/W ₀ ] × 100%
It can be seen that the obtained electrolyte retention ratio not only characterized the capacity of the separator to accommodate the electrolyte, but also embodied the ability of the separator to retain the electrolyte.

The evaluation results of Test Examples 1 and 2 are summarized in Table 1. Table 1 shows the basic unit chemical formula and defect percentage of the coating used for each separator.

Table 1

Test example 3
In this test example, the injection time of each battery cell is evaluated. Specifically, the electrolytic solution is injected into the battery cell by vacuum injection, and the electrolytic solution is sufficiently transferred from the discrete state to the inside of the separator, and also transferred to the inside of the positive and negative electrode plates to completely infiltrate the battery cell. In addition to recording the time required until the end of the cycle, it is required that the battery cell obtained as a premise has normal performance (the phenomenon of sudden drop in performance due to lack of electrolyte does not occur within 100 cycles).

Test example 4
In this test example, the rate performance of each battery cell is evaluated. Specifically, the battery cells were placed in an Arbin electrochemical workstation test channel and subjected to constant current charging at a rate of 0.1 C to a charge termination voltage of 4 V, followed by constant voltage charging for 30 minutes, followed by 0 Constant current discharge is performed at rates of 1C and 1C until the final discharge voltage reaches 2.5V, and the discharge capacity is recorded as 0.1C capacity and 1C capacity, respectively. Calculate the rate performance based on the following formula:
Rate performance = 1C capacity/0.1C capacity x 100%.

Test example 5
In this test example, the cycle performance of each battery cell is evaluated. Specifically, the battery cells were placed in an Arbin electrochemical workstation test channel, charged at a constant current at a rate of 1C until the end-of-charge voltage reached 4V, allowed to stand for 5 minutes, and then discharged at a rate of 1C. Constant current discharge to 2.5 V, record the discharge capacity, allow to stand for another 5 minutes, and repeat such cycle 100 times. Cycle performance is calculated based on the following formula.
Cycle performance = 100th cycle capacity/1st cycle capacity x 100%.

By way of example, the cycle performance graphs of the battery cells of Control Application 1, Comparative Application 1 and Application 1 are shown in FIG.

The evaluation results of Test Examples 3 to 5 are summarized in Table 2. Also shown in Table 2 are the chemical formulas and defect percentages of the base units of the coatings used for each separator.

Table 2

As can be seen from the results of each of the above tests, from the results shown in Table 1, compared to the bare film to which no coating was applied in Control Example 1 and the separator to which the alumina coating was applied in Control Example 2, Comparative Examples 1 to 7 and Examples 1 to 20 were found to have improved performance in terms of electrolyte wettability and electrolyte retention rate. However, in Comparative Examples 1 to 7, there is a limit to the performance improvement of the separator. Accordingly, from the results shown in Table 2, it was found that the battery cells of Comparative Application Examples 1 to 7 each containing these separators have limitations in improving the battery cell injection time, rate performance, and cycle performance. .

In comparison, in Examples 1 to 20, the coatings of the defective organic-inorganic hybrid complexes of the present application were applied, and the separators having the coatings showed excellent performance in terms of electrolyte wettability and electrolyte retention rate. has improved significantly. Accordingly, the battery cells of Application Examples 1 to 20 each containing these separators were significantly improved in the battery cell injection time, rate performance, and cycle performance.

In Examples 1-16, several exemplary hybrid organic-inorganic complexes included in the separator coating were introduced with ligand defects within the percent defect ranges specified in this application.

From the results shown in Table 1, compared to Comparative Example 1 using a defect-free organic-inorganic hybrid complex (CN) ₃ Fe·Na, the separators of Examples 1 to 5 had better electrolyte wettability and electrolyte solution wettability. It was found that the performance in terms of retention was significantly superior. Accordingly, from the results shown in Table 2, the battery cells of Application Examples 1 to 5 each containing these separators were superior to the battery cell of Comparative Application Example 1 in terms of the battery cell injection time, rate performance, and cycle performance. It was also found to be significantly superior in

Similarly, from the results shown in Table 1, the separators of Examples 9 to 13 are superior to Comparative Example 4, which uses a defect-free organic-inorganic hybrid complex (cbIm) ₂ Co. It was found that the performance in terms of retention rate was significantly excellent. It was found that the battery cell injection time, rate performance, and cycle performance were significantly superior to the cell.

Further, from the results shown in Table 1, the corresponding defect-free organic-inorganic hybrid complexes (BTC) ₂ Cu ₃ ·K and (BDC)[Fe(OH) _0.8 F _{0 ]} in Comparative Examples 5 to 7, respectively. _.2 ]·Li _0.5 and (NTB) ₂ [Zn ₄ O]·Mg _0.1 , the separators of Examples 14-16 show better performance in terms of electrolyte wettability and electrolyte retention. was found to be significantly superior. Accordingly, from the results shown in Table 2, it can be seen that the battery cells of Application Examples 14 to 16 containing these separators, respectively, have a longer battery cell injection time, rate performance and cycle performance than the battery cells of Comparative Application Examples 5 to 7. It was found to be remarkably excellent in both.

As can be seen from this, the organic-inorganic hybrid complex is introduced with ligand defects within the defect percentage range specified in this application to provide an electrolyte solution with the organic-inorganic hybrid complex as a separator coating material. By significantly promoting the wettability improvement effect and improving the electrolyte retention rate, the battery cell injection rate, and the rate performance and cycle performance of the battery cell can be improved. The performance improvements described above by introducing defects into hybrid organic-inorganic complexes can be broadly applied to a number of different metals and/or ligands.

Of particular note, when using the same ligand (CN) and the same metal (Fe) and differing only in the defect percentage of the introduced defects, the results shown in Table 1 show relatively low defect percentages. Compared to Comparative Example 2 and Comparative Example 3, which has a relatively high defect percentage, in Examples 1-5, the defect percentage in the organic-inorganic hybrid complex contained in the separator coating is limited to 1-30% in the present application. It was found that the separator has remarkably excellent performance in terms of electrolyte wettability and electrolyte retention rate. Accordingly, from the results shown in Table 2, it can be seen that the battery cells of Application Examples 1 to 5 each containing these separators had better battery cell injection time, rate performance and cycle performance than the battery cells of Comparative Application Examples 2 and 3. It was found to be remarkably excellent in both.

In Examples 17-20, the battery cells were tested under the premise that a coating additionally loaded with alumina (Al ₂ O ₃ ) was applied to the separator to ensure that the wettability properties of the separator were within reasonable limits. 's rate performance and cyclability are even better. The reason is that after the organic-inorganic hybrid complex is mixed with Al ₂ O ₃ , the complementarity between the particle morphologies allows the two to bind more tightly, and the organic-inorganic hybrid complex exhibits infiltration properties. Al ₂ O ₃ can provide a separator structure with stable rigidity, and both have a synergistic effect. and achieve the optimum synergistic effect at the mixing ratio adopted in Example 18.

INDUSTRIAL APPLICABILITY The defective organic-inorganic hybrid complex of the present application has the effect of improving the electrolyte wettability of the separator when applied to the coating of the separator for secondary batteries, and the electrolysis of the separator. By improving the liquid retention rate, polarization can be reduced and the rate performance and cycle life of the secondary battery can be improved. Therefore, the present application is suitable for industrial use.

1 battery pack 2 upper housing 3 lower housing 4 battery module 5 secondary battery 51 case 52 electrode assembly 53 top cover assembly

Claims (21)

an organic-inorganic hybrid complex, wherein the organic-inorganic hybrid complex is constructed by periodically assembling basic units represented by the formula (I) along at least one spatial direction;
[L _x−i □ _i ][M _a C _b ]·A _z (I)
In formula (I),
M represents the first transition metal element,
C optionally represents an atom, group, or anion capable of forming a metal cluster with M;
L represents an organic bridging ligand that forms a coordinate bond with the metal M or the metal cluster M _a C _b ,
□ represents a ligand defect,
A represents an atom or cation that can be occluded and released,
x takes a number from 1 to 4, and optionally takes a number from 1 to 3;
a takes a number greater than 0 and less than or equal to 4, and optionally from 1 to 4;
z ranges from 0 to 2, and optionally from 0 to 1;
0<i<x and 0≤b:a≤1;
The organic-inorganic hybrid complex, wherein the defect degree of said organic-inorganic hybrid complex is represented by defect percentage i/x*100%, and said defect percentage is from 1% to 30%. Organic-inorganic hybrid according to claim 1, wherein the defect percentage is between 2% and 20%, optionally between 2.5% and 18%, further optionally between 5% and 10%. Complex. 3. The organic-inorganic hybrid complex according to claim 1, wherein 1/2≦x:a≦3. 4. The organic-inorganic hybrid complex according to any one of claims 1 to 3, wherein 1/4≤b:a≤1. Said M is selected from one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, and optionally Mn, Fe, Co, Cu and Zn The organic-inorganic hybrid complex according to any one of claims 1 to 4, which is selected from one or more of C is selected from one or more of -O-, =O, O ^2- , S ^2- , F ^- , Cl ^- , Br ^- , I ^- , CO, -OH and OH ^- , and optionally Optionally, the organic-inorganic hybrid complex according to any one of claims 1 to 5, which is -O- or -OH. L is a cyano group, benzimidazole ligand, porphyrin ligand, pyridine ligand, pyrazole ligand, pyrimidine ligand, piperidine ligand, pyrrolidine ligand, furan ligands, thiophene ligands, pyrazine ligands, piperazine ligands, pyridazine ligands, triazine ligands, tetrazine ligands, indole ligands, quinoline ligands morpholine-based ligands, carbazole-based ligands and polycarboxylic acid-based ligands, wherein one or more hydrogen atoms in said L are optionally is substituted with one or more substituents, each of which is a cyano group, a nitro group, an amino group, an aldehyde group, a carboxyl group, a halogen, a C1-C6 alkyl group, a C1-C6 hydroxyalkyl group, a C1 - independently from at least one of a C6 alkoxy group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C8 cycloalkyl group, a C6-C10 aryl group, a C6-C10 heteroaryl group, and any combination thereof; optionally, L is selected from a cyano group, at least one of a benzimidazole-based ligand and a polycarboxylic acid-based ligand, and further optionally, L is a cyano group , benzimidazole-based ligands, trimesic acid-based ligands and terephthalic acid-based ligands, and optionally, L is a cyano group, 5-chlorobenzimidazole coordination (cbIm), a trimesic acid ligand (BTC), a terephthalic acid ligand (BDC) and at least one of a tris(2-benzimidazolemethyl)amine ligand (NTB). Item 7. The organic-inorganic hybrid complex according to any one of Items 1 to 6. said A is selected from atoms or cations of one or more of the metallic elements Li, Na, K, Rb, Cs, Sr, Zn, Mg and Ca, and is further optionally Li or Na; The organic-inorganic hybrid complex according to any one of claims 1 to 7. The basic units represented by formula (I) are assembled periodically along at least one of three spatial directions X', Y' and Z', and the three directions X', Y' and Z ' forms an angle between 0 and 75 degrees, optionally between 5 and 60 degrees, with the X, Y and Z directions of a Cartesian coordinate system, respectively. The organic-inorganic hybrid complex according to item 1. Organic-inorganic according to claim 9, wherein the basic units of formula (I) are assembled periodically along at least one spatial direction of the X, Y and Z directions of a Cartesian coordinate system. Hybrid complex. 11. Organic- according to any one of claims 1 to 10, wherein the number by which the basic units of formula (I) are periodically assembled along at least one spatial direction is from 3 to 10,000. Inorganic hybrid complex. A coating composition comprising an organic-inorganic hybrid complex according to any one of claims 1-11. Based on the weight of the coating composition, the content of the organic-inorganic hybrid complex is from 12 wt% to 90 wt%, optionally from 17 wt% to 85 wt%, further optionally from 34 wt%. 13. The coating composition of claim 12, which is 68 wt%. 14. A coating composition according to claim 12 or 13, further comprising inorganic particles. The mass ratio of the organic-inorganic hybrid complex to the total mass of the organic-inorganic hybrid complex and the inorganic particles in the coating composition is from 15 wt% to 85 wt%, optionally from 20 wt%. 15. A coating composition according to claim 14, which is 80 wt%, and optionally from 40 wt% to 80 wt%. The inorganic particles include at least one of boehmite, zeolite, molecular sieves, alumina, aluminum oxyhydroxide, silicon dioxide, aluminum nitride, silicon carbide, magnesium oxide, calcium oxide, zinc oxide, zirconium oxide, titanium oxide, and mixtures thereof. 16. The coating composition of claim 14 or 15, selected from A separator for a secondary battery,
a polymer substrate layer;
a coating applied to the polymer substrate layer comprising the organic-inorganic hybrid complex according to any one of claims 1 to 11 or the coating composition according to any one of claims 12 to 16; A separator for a secondary battery, including a secondary battery,
a positive electrode;
a negative electrode;
an electrolyte;
A secondary battery comprising the secondary battery separator according to claim 17 . A battery module comprising the secondary battery according to claim 18 . A battery pack comprising the battery module of claim 19 . A power consumption device comprising the secondary battery according to claim 18, the battery module according to claim 19, the battery pack according to claim 20, or a combination thereof.

Images